CN102268137A - Star-shaped polylactic acid-poly(dimethylaminoethyl methacrylate) amphiphilic segmented copolymer and preparation method thereof - Google Patents
Star-shaped polylactic acid-poly(dimethylaminoethyl methacrylate) amphiphilic segmented copolymer and preparation method thereof Download PDFInfo
- Publication number
- CN102268137A CN102268137A CN 201110119598 CN201110119598A CN102268137A CN 102268137 A CN102268137 A CN 102268137A CN 201110119598 CN201110119598 CN 201110119598 CN 201110119598 A CN201110119598 A CN 201110119598A CN 102268137 A CN102268137 A CN 102268137A
- Authority
- CN
- China
- Prior art keywords
- poly
- star
- lactic acid
- reaction
- azide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention relates to a star-shaped polylactic acid-poly(dimethylaminoethyl methacrylate) amphiphilic segmented copolymer and a preparation method thereof. Butynol 2-bromoisobutyrate produced through an esterification reaction of butynol and 2-bromoisobutyryl bromide is utilized as an initiator. Cuprous bromide and 1,4,7,10,10-hexamethyltriethylenetetramine compose a catalyst system and through an atom transfer free radical polymerization reaction, alkynyl-terminiated poly(dimethylaminoethyl methacrylate) is synthesized. An azide functional group-containing polylactic acid is synthesized through a lactide ring-opening polymerisation method in the presence of pentaerythritol triazide as an initiator and stannous octoate as a catalyst. Through click chemistry, poly(dimethylaminoethyl methacrylate) (PDMAEMA) arms and the azide functional group-containing polylactic acid are coupled to form an AB3 type star-shaped polylactic acid-poly(dimethylaminoethyl methacrylate) amphiphilic segmented copolymer (SPLA-b-PDMAEMA). The star-shaped polylactic acid-poly(dimethylaminoethyl methacrylate) amphiphilic segmented copolymer has good biocompatibility and stability, is a potential carrier capable of carrying genes and drugs synchronously, and has good prospects of application in antitumor drug carriers.
Description
Technical field
The invention belongs to molecular biosciences medical material field, be specifically related to a kind of preparation method who can be used for transmitting simultaneously the star polymer of chemotherapeutics and gene.
Background technology
Poly(lactic acid) is one of maximum Biodegradable material of research at present, it is a kind of nontoxic, non-irritating Biodegradable Materials, its main chain contains unstable easily being hydrolyzed or the chemical bond of enzymolysis, degradation in vivo is that lactic acid can participate in body metabolism, discharge in the Yi Congti and do not put aside, have low immunogenicity and excellent biological compatibility, can be used safely in the body, therefore, be often used as biodegradable pharmaceutical carrier.
Dimethylaminoethyl methacrylate (DMAEMA) is a kind of multi-functional water-soluble monomer, has the characteristic of alkene, aminated compounds, can be used as non-water dispersible static inhibitor, chlorine-containing polymer stablizer, emulsifying agent and precipitated cationic agent etc.With DMAEMA is the polymer molecule that monomer can synthesize size and valence state homogeneous, and superpolymer PDMAEMA prepared therefrom demonstrates pH and temperature-responsive and excellent biological compatibility in the aqueous solution.There are hydrophilic tertiary amine groups, carbonyl and hydrophobic alkyl group in the PDMAEMA molecular structure simultaneously, and two class groups match each other on space structure, when system temperature or pH change, can cause the formation and the destruction of hydrogen bond, thereby produce the variation of polymer phase.
Polymethyl acrylic acid dimethylaminoethyl (PDMAEMA) is as genophore, and affinity DNA plays the media transfer function in different cells well, and it also is a kind of effective transfection body.It can protect plasmid by nuclease degradation; and during cell transfecting and the reaction of cytolemma less; have biocompatibility, anticoagulation function; can be widely used in drug targeting and slowly-releasing, DNA and transmit aspects such as carrier and biocompatible materials, so it there is wide application prospect on biomedical material.
The macromolecule micelle of can spontaneous formation after amphipathic nature block polymer dissolves in water forming by wetting ability shell and hydrophobic cores, the micella diameter the nano level scope (＜200nm), what hydrophobic block was formed endorses with as little Drug Storage, finishes solubilising and parcel to medicine.Because most drug is hydrophobic, they can be attached to by the mode of chemical bonding or physically trapping in the micellar nuclear, form the nanometer polymer micelle carrier system.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of star poly(lactic acid)-polymethyl acrylic acid dimethylaminoethyl amphipathic nature block polymer, it is in conjunction with ring-opening polymerization method, Transfer Radical Polymerization and click chemistry method, having synthesized star amphipathic lactic acid-b-polymethyl acrylic acid dimethylaminoethyl segmented copolymer, is a kind of star amphipathic nature polyalcohol of hydrophilic segment cation group.This multipolymer is endorsed with bag and is carried a hydrophobicity chemotherapeutics, and the segment of band cation group can the static complex gene, thereby realizes chemotherapeutics and gene same year.
The structural formula of described multipolymer is as follows:
Wherein:
Technical scheme of the present invention: the preparation method of star poly(lactic acid)-polymethyl acrylic acid dimethylaminoethyl amphipathic nature block polymer, can adopt following steps:
A) Terminal Acetylenes base PDMAEMA's is synthetic
Get 0.1～10ml butynol and 0.1～15ml 2-bromine isobutyl acylbromide is dissolved in 1～100ml ethylene dichloride, add 0.1～5ml triethylamine, react 1～5h under the condition of ice bath, synthesized Terminal Acetylenes base small molecules initiator; The dimethylaminoethyl methacrylate of getting 1～10g joins in the container, by [initiator]/[CuBr]/[part]=1: 0.1～10: 0.1～20 proportionings, add the front synthetic again and contain initiator, the catalyzer cuprous bromide and 1,4 of Terminal Acetylenes base, 7,10,10-hexamethyl Triethylenetetramine (TETA) (HMTETA), under the condition of anhydrous and oxygen-free, polymerization temperature is 50～80 ℃, reacted 15～30 hours, the polymethyl acrylic acid dimethylaminoethyl that contains the Terminal Acetylenes base has been synthesized in reaction;
More than Fan Ying equation is as follows:
B) the synthetic azide poly(lactic acid) of ring-opening polymerization method
Carry out the preparation of azide tribromoneoamyl alcohol earlier, get 0.1～5.0g tribromoneoamyl alcohol and 0.1～10g sodiumazide is dissolved in 10～100mlN, in the dinethylformamide (DMF), logical rare gas element, react 1～5d down at 50～80 ℃, obtain the tribromoneoamyl alcohol of azide; Get the dry D that crosses of 1～10g then, the L-rac-Lactide places reaction tubes, with the azide tribromoneoamyl alcohol is initiator, stannous octoate is that (catalyst consumption is 100～2000 with lactide monomer molar mass ratio to catalyzer: 1), reaction tubes places under 100～150 ℃, react 10～15h under inert gas atmosphere, ring-opening polymerization prepares the poly(lactic acid) of azide, the poly(lactic acid) of azide
1The H-NMR spectrogram is seen accompanying drawing 1;
More than Fan Ying equation is as follows:
C) the synthetic star PLA-b-PDMAEMA polymkeric substance of click chemistry method
In the mol ratio of azide poly(lactic acid)/CuBr/ part is that 1: 3～10: 5～20 ratio joins azide poly(lactic acid), cuprous bromide and part in the reaction tubes, add the excessive PDMAEMA that contains the Terminal Acetylenes base again, 5～20ml tetrahydrofuran (THF), reaction tubes vacuumized be placed in the oil bath 30～60 ℃ of reaction 10～20h, synthesized AB
3Type star amphipathic lactic acid-b-polymethyl acrylic acid dimethylaminoethyl segmented copolymer, the multipolymer of various brachiums
1The H-NMR spectrogram is seen accompanying drawing 2;
Above reaction process is as follows:
With respect to scheme of the prior art, advantage of the present invention is:
The raw material sources that technical solution of the present invention adopts are extensive; That the synthetic radial copolymer possesses simultaneously is amphipathic, biocompatibility, degradable character; Because the lower hydrodynamic volume of star polymer, the particulate that utilizes this radial copolymer to prepare has better stability, helps sealing and transmitting of medicine; The shell of band cation group can the static complex gene, reaches the effect of transmitting gene, thus realize medicine and gene with year.
Description of drawings
Fig. 1 is the poly(lactic acid) that contains three nitrine end groups
1The H-NMR spectrogram
Fig. 2 is for the PLA-b-PDMAEMA's of the different brachiums that prepare among the embodiment
1The H-NMR spectrogram
Fig. 3 is the PLA-b-PDMAEMA nanoparticle TEM photo of embodiment 1 preparation
Embodiment
Below in conjunction with specific embodiment such scheme is described further.Should be understood that these embodiment are used to the present invention is described and are not limited to limit the scope of the invention.
Embodiment 1 polymethyl acrylic acid dimethylaminoethyl molecular weight is the preparation of 4000 star polymer
(1) the polymethyl acrylic acid dimethylaminoethyl of the synthetic Terminal Acetylenes base of ATRP method:
(a) get the 1ml butynol and 10ml 2-bromine isobutyl acylbromide is dissolved in the 15ml ethylene dichloride, add the 1.84ml triethylamine, react 3h under the condition of ice bath, synthesized Terminal Acetylenes base small molecules initiator, purification obtains colourless transparent liquid, and sealing is deposited to the moisture eliminator standby in the bottle of packing into;
(b) getting 4.0g dimethylaminoethyl methacrylate (DMAEMA) adds in the reaction tubes, by [initiator]/[CuBr]/[part]=1: 1: 1.2 proportioning, add the front synthetic again and contain the initiator of Terminal Acetylenes base, catalyzer cuprous bromide and 1,4,7,10,10-hexamethyl Triethylenetetramine (TETA) (HMTETA), under vacuum condition, 60 ℃ of reaction 20h, the polymethyl acrylic acid dimethylaminoethyl that has synthesized the Terminal Acetylenes base, add a large amount of tetrahydrofuran (THF) dilution termination reactions, solution is crossed the pillar of filling with neutral aluminium sesquioxide particle (100～200 order), remove mantoquita and some complex compounds in the product polymkeric substance, revolve the steaming back and precipitate in the normal hexane of ice, vacuum-drying 48h gets white solid product;
(2) ring-opening polymerization method is synthesized the azide poly(lactic acid):
(a) carry out the preparation of azide tribromoneoamyl alcohol earlier, get the 5g tribromoneoamyl alcohol and the 6g sodiumazide is dissolved in 30ml N, in the dinethylformamide (DMF), logical nitrogen is at 70 ℃ of reaction 3d down, with three complete azides of bromine atoms in the tribromoneoamyl alcohol; After reaction stops, obtaining product and remove by filter excessive unreacted sodiumazide earlier, N is removed in underpressure distillation again, dinethylformamide, be dissolved into then in the purified methylene dichloride, extraction removes the Sodium Bromide of reaction generation and residual solvent N, dinethylformamide for three times in deionized water; An amount of Calcium Chloride Powder Anhydrous particle is joined in the above-mentioned dichloromethane solution, stop heating behind 50 ℃ of reflux 12h, be cooled to room temperature, remove by filter calcium chloride, gained liquid is as clear as crystal, revolves to steam to remove chloroform, obtains product and deposits in the vacuum drying oven dry;
(b) get the dry D that crosses of 6g, the L-rac-Lactide places reaction tubes, to reaction tubes vacuumize successively, applying argon gas, with the azide tribromoneoamyl alcohol is initiator, stannous octoate is catalyzer (catalyst consumption is 500: 1 with lactide monomer molar mass ratio), under the anhydrous and oxygen-free condition, under 130 ℃, reaction 12h, ring-opening polymerization prepares the poly(lactic acid) of azide.Open reaction tubes after reaction finishes, add chloroform and be diluted to suitable concentration, precipitate in a large amount of anhydrous methanols, repetitive operation is placed on dry 48h in vacuum drying oven for three times, obtains slightly yellow solid;
(3) the synthetic star PLA-b-PDMAEMA polymkeric substance of click chemistry method:
In the mol ratio of azide poly(lactic acid)/CuBr/ part is that 1: 3.3: 9.9 ratio joins azide poly(lactic acid), cuprous bromide and part in the reaction tubes; add the excessive PDMAEMA that contains the Terminal Acetylenes base again; under argon shield, add the 8ml tetrahydrofuran (THF); under vacuumizing, reaction tubes is sealed; be placed on 35 ℃ of reaction 12h in the oil bath, synthesized AB
3Type star amphipathic lactic acid-b-polymethyl acrylic acid dimethylaminoethyl segmented copolymer.
The polymkeric substance for preparing is with a wide range of applications in fields such as drug sustained release system, organizational process and packings.With the particulate of this polymkeric substance for preparing by self-assembly acquisition nano-scale, the TEM picture is seen accompanying drawing 3, and it can be used for the transmission of medicine and gene.
Embodiment 2 polymethyl acrylic acid dimethylaminoethyl molecular weight are the preparation of 6000 star polymer
(1) the polymethyl acrylic acid dimethylaminoethyl of the synthetic Terminal Acetylenes base of ATRP method:
(a) get the 0.1ml butynol and 0.1ml 2-bromine isobutyl acylbromide is dissolved in the 1ml ethylene dichloride, add the 1ml triethylamine, react 5h under the condition of ice bath, synthesized Terminal Acetylenes base small molecules initiator, purification obtains colourless transparent liquid, and sealing is deposited to the moisture eliminator standby in the bottle of packing into;
(b) get 6.0g dimethylaminoethyl methacrylate (DMAEMA) in reaction tubes, by [initiator]/[CuBr]/[part]=1: 0.1: 0.1 proportioning, the adding synthetic contains the initiator of Terminal Acetylenes base, the catalyzer cuprous bromide, 1,4,7,10,10-hexamethyl Triethylenetetramine (TETA) (HMTETA), under vacuum condition, 50 ℃ of reaction 30h, the polymethyl acrylic acid dimethylaminoethyl that has synthesized the Terminal Acetylenes base, add a large amount of tetrahydrofuran (THF) dilution termination reactions, solution is crossed the pillar of filling with neutral aluminium sesquioxide particle (100～200 order), remove mantoquita and some complex compounds in the product polymkeric substance, revolve the steaming back and precipitate in the normal hexane of ice, vacuum-drying 48h gets white solid product.
(2) ring-opening polymerization method is synthesized the azide poly(lactic acid):
(a) carry out the preparation of azide tribromoneoamyl alcohol earlier, get the 0.1g tribromoneoamyl alcohol and the 0.1g sodiumazide is dissolved in 10ml N, in the dinethylformamide (DMF), logical nitrogen is at 50 ℃ of reaction 5d down, with three complete azides of bromine atoms in the tribromoneoamyl alcohol; After reaction stops, obtaining product and remove by filter excessive unreacted sodiumazide earlier, N is removed in underpressure distillation again, dinethylformamide, be dissolved into then in the purified methylene dichloride, extraction removes the Sodium Bromide of reaction generation and residual solvent N, dinethylformamide for three times in deionized water; An amount of Calcium Chloride Powder Anhydrous particle is joined in the above-mentioned dichloromethane solution, stop heating behind 50 ℃ of reflux 12h, be cooled to room temperature, remove by filter calcium chloride, gained liquid is as clear as crystal, revolves to steam to remove chloroform, obtains product and deposits in the vacuum drying oven dry;
(b) get the dry D that crosses of 1g, the L-rac-Lactide places reaction tubes, to reaction tubes vacuumize successively, applying argon gas, be initiator with the azide tribromoneoamyl alcohol, stannous octoate is a catalyzer, catalyst consumption is 100: 1 with lactide monomer molar mass ratio; Under the anhydrous and oxygen-free condition, under 100 ℃, reaction 15h, ring-opening polymerization prepares the poly(lactic acid) of azide.Open reaction tubes after reaction finishes, add chloroform and be diluted to suitable concentration, precipitate in a large amount of anhydrous methanols, repetitive operation is placed on dry 48h in vacuum drying oven for three times, obtains slightly yellow solid.
(3) the synthetic star PLA-b-PDMAEMA polymkeric substance of click chemistry method: in the mol ratio of azide poly(lactic acid)/CuBr/ part is that 1: 3: 5 ratio joins azide poly(lactic acid), cuprous bromide and part in the reaction tubes; add the excessive PDMAEMA that contains the Terminal Acetylenes base again; under argon shield, add the 5ml tetrahydrofuran (THF); under vacuumizing, reaction tubes is sealed; be placed on 30 ℃ of reaction 20h in the oil bath, synthesized AB
3Type star amphipathic lactic acid-b-polymethyl acrylic acid dimethylaminoethyl segmented copolymer.
(1) the polymethyl acrylic acid dimethylaminoethyl of the synthetic Terminal Acetylenes base of ATRP method:
(a) get the 10ml butynol and 15ml 2-bromine isobutyl acylbromide is dissolved in the 100ml ethylene dichloride, add the 5ml triethylamine, react 1h under the condition of ice bath, synthesized Terminal Acetylenes base small molecules initiator, purification obtains colourless transparent liquid, and sealing is deposited to the moisture eliminator standby in the bottle of packing into;
(b) get 8.0g dimethylaminoethyl methacrylate (DMAEMA) in reaction tubes, by [initiator]/[CuBr]/[part]=1: 10: 20 proportioning, add a certain amount of synthetic and contain the initiator of Terminal Acetylenes base, the catalyzer cuprous bromide, 1,4,7,10,10-hexamethyl Triethylenetetramine (TETA) (HMTETA), under vacuum condition, 80 ℃ of reaction 15h, the polymethyl acrylic acid dimethylaminoethyl that has synthesized the Terminal Acetylenes base, add a large amount of tetrahydrofuran (THF) dilution termination reactions, solution is crossed the pillar of filling with neutral aluminium sesquioxide particle (100～200 order), remove mantoquita and some complex compounds in the product polymkeric substance, revolve the steaming back and precipitate in the normal hexane of ice, vacuum-drying 48h gets white solid product.
(2) ring-opening polymerization method is synthesized the azide poly(lactic acid):
(a) carry out the preparation of azide tribromoneoamyl alcohol earlier, get the 5.0g tribromoneoamyl alcohol and the 10.0g sodiumazide is dissolved in 100mlN, in the dinethylformamide (DMF), logical nitrogen is at 80 ℃ of reaction 1d down, with three complete azides of bromine atoms in the tribromoneoamyl alcohol; After reaction stops, obtaining product and remove by filter excessive unreacted sodiumazide earlier, N is removed in underpressure distillation again, dinethylformamide, be dissolved into then in the purified methylene dichloride, extraction removes the Sodium Bromide of reaction generation and residual solvent N, dinethylformamide for three times in deionized water; An amount of Calcium Chloride Powder Anhydrous particle is joined in the above-mentioned dichloromethane solution, stop heating behind 50 ℃ of reflux 12h, be cooled to room temperature, remove by filter calcium chloride, gained liquid is as clear as crystal, revolves to steam to remove chloroform, obtains product and deposits in the vacuum drying oven dry;
(b) get the dry D that crosses of 10.0g, the L-rac-Lactide places reaction tubes, to reaction tubes vacuumize successively, applying argon gas, be initiator with the azide tribromoneoamyl alcohol, stannous octoate is a catalyzer, catalyst consumption is 2000: 1 with lactide monomer molar mass ratio; Under the anhydrous and oxygen-free condition, under 150 ℃, reaction 10h, ring-opening polymerization prepares the poly(lactic acid) of azide.Open reaction tubes after reaction finishes, add chloroform and be diluted to suitable concentration, precipitate in a large amount of anhydrous methanols, repetitive operation is placed on dry 48h in vacuum drying oven for three times, obtains slightly yellow solid.
(3) the synthetic star PLA-b-PDMAEMA polymkeric substance of click chemistry method: in the mol ratio of azide poly(lactic acid)/CuBr/ part is that 1: 10: 20 ratio joins azide poly(lactic acid), cuprous bromide and part in the reaction tubes; add the excessive PDMAEMA that contains the Terminal Acetylenes base again; under argon shield, add the 20ml tetrahydrofuran (THF); under vacuumizing, reaction tubes is sealed; be placed on 60 ℃ of reaction 10h in the oil bath, synthesized AB
3Type star amphipathic lactic acid-b-polymethyl acrylic acid dimethylaminoethyl segmented copolymer.
Claims (5)
1. the preparation method of star poly(lactic acid)-polymethyl acrylic acid dimethylaminoethyl amphipathic nature block polymer is characterized in that the structural formula of described multipolymer is as follows:
Wherein:
2. the preparation method of the poly(lactic acid) of the star in the claim 1-polymethyl acrylic acid dimethylaminoethyl amphipathic nature block polymer is characterized in that described method comprises the following steps:
(1) the polymethyl acrylic acid dimethylaminoethyl of the synthetic Terminal Acetylenes base of ATRP method: get 0.1～10ml butynol and 0.1～15ml 2-bromine isobutyl acylbromide is dissolved in 1～100ml ethylene dichloride, add 0.1～5ml triethylamine, react 1～5h under the condition of ice bath, synthesized Terminal Acetylenes base small molecules initiator; The dimethylaminoethyl methacrylate of getting 1～10g joins in the container, by [initiator]/[CuBr]/[part]=1: 0.1～10: 0.1～20 proportionings, add the front synthetic again and contain initiator, the catalyzer cuprous bromide and 1,4 of Terminal Acetylenes base, 7,10,10-hexamethyl Triethylenetetramine (TETA) (HMTETA), under the condition of anhydrous and oxygen-free, polymerization temperature is 50～80 ℃, reacted 15～30 hours, the polymethyl acrylic acid dimethylaminoethyl that contains the Terminal Acetylenes base has been synthesized in reaction;
(2) ring-opening polymerization method is synthesized the azide poly(lactic acid): 0.1～5.0g tribromoneoamyl alcohol and 0.1～10g sodiumazide are dissolved in 10～100mlN, in the dinethylformamide (DMF), logical rare gas element reacts 1～5d down at 50～80 ℃, with three complete azides of bromine atoms in the tribromoneoamyl alcohol; Then with the dry D that crosses of 1～10g, the L-rac-Lactide places reaction tubes, with front synthetic azide tribromoneoamyl alcohol is initiator, stannous octoate is that (catalyst consumption is 100～2000 with lactide monomer molar mass ratio to catalyzer: 1), under 100～150 ℃, reaction 10～15h, reaction obtains the poly(lactic acid) of azide;
(3) the synthetic star PLA-b-PDMAEMA polymkeric substance of click chemistry method: in the mol ratio of azide poly(lactic acid)/CuBr/ part is that 1: 3～10: 5～20 ratio joins azide poly(lactic acid), cuprous bromide and part in the reaction tubes, add the excessive PDMAEMA that contains the Terminal Acetylenes base again, 5～20ml tetrahydrofuran (THF), reaction tubes vacuumized be placed in the oil bath 30～60 ℃ of reaction 10～20h, synthesized AB3 type star amphipathic lactic acid-b-polymethyl acrylic acid dimethylaminoethyl segmented copolymer.
3. preparation method according to claim 2 is characterized in that the butynol described in the step (1) can replace with other alcohol that contains alkynyl, can be selected from propiolic alcohol, methylparafynol, dimethylated hexynol etc.
4. preparation method according to claim 2 is characterized in that passing through described in the step (1) changes monomer DMAEMA and the initial feed ratio of small molecules initiator, can obtain the radial copolymer of a series of different brachiums.
5. preparation method according to claim 2 is characterized in that the azide poly(lactic acid) that can obtain different molecular weight by the change reaction conditions described in the step (2), and its molecular weight control is 2000～20000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110119598 CN102268137A (en) | 2011-05-10 | 2011-05-10 | Star-shaped polylactic acid-poly(dimethylaminoethyl methacrylate) amphiphilic segmented copolymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110119598 CN102268137A (en) | 2011-05-10 | 2011-05-10 | Star-shaped polylactic acid-poly(dimethylaminoethyl methacrylate) amphiphilic segmented copolymer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102268137A true CN102268137A (en) | 2011-12-07 |
Family
ID=45050612
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110119598 Pending CN102268137A (en) | 2011-05-10 | 2011-05-10 | Star-shaped polylactic acid-poly(dimethylaminoethyl methacrylate) amphiphilic segmented copolymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102268137A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103374106A (en) * | 2012-04-20 | 2013-10-30 | 中国科学院上海有机化学研究所 | Structure-controllable polymethylene macro-molecule initiating agent and preparation method and application thereof |
| CN104629059A (en) * | 2015-01-28 | 2015-05-20 | 同济大学 | Preparation method of temperature response type polymer for controlled drug release and genetic vectors |
| JP2017057380A (en) * | 2015-09-15 | 2017-03-23 | Jsr株式会社 | Curable composition, cured film, display element and solid- state imaging device, and compound |
| CN106750343A (en) * | 2016-12-25 | 2017-05-31 | 河南师范大学 | Y type amphiphilic block copolymers and preparation method thereof and with the copolymer be carrier targeting intracellular drug release carrier micelle |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090054619A1 (en) * | 2007-08-24 | 2009-02-26 | Board Of Trustees Of Michigan State University | Functionalization of polyglycolides by "click" chemistry |
| CN101503497A (en) * | 2009-03-02 | 2009-08-12 | 江南大学 | Preparation of star type block acid sensitive nano micelle |
-
2011
- 2011-05-10 CN CN 201110119598 patent/CN102268137A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090054619A1 (en) * | 2007-08-24 | 2009-02-26 | Board Of Trustees Of Michigan State University | Functionalization of polyglycolides by "click" chemistry |
| CN101503497A (en) * | 2009-03-02 | 2009-08-12 | 江南大学 | Preparation of star type block acid sensitive nano micelle |
Non-Patent Citations (1)
| Title |
|---|
| 《macromolecular rapid communications》 20080601 Philippe Lecomte, Raphaël Riva, Christine Jérôme, Robert Jérôme Macromolecular Engineering of Biodegradable Polyesters by Ring-Opening Polymerization and 'Click' Chemistry 第982-997页 1-5 第29卷, 第12-13期 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103374106A (en) * | 2012-04-20 | 2013-10-30 | 中国科学院上海有机化学研究所 | Structure-controllable polymethylene macro-molecule initiating agent and preparation method and application thereof |
| CN104629059A (en) * | 2015-01-28 | 2015-05-20 | 同济大学 | Preparation method of temperature response type polymer for controlled drug release and genetic vectors |
| CN104629059B (en) * | 2015-01-28 | 2017-02-22 | 同济大学 | Preparation method of temperature response type polymer for controlled drug release and genetic vectors |
| JP2017057380A (en) * | 2015-09-15 | 2017-03-23 | Jsr株式会社 | Curable composition, cured film, display element and solid- state imaging device, and compound |
| CN106750343A (en) * | 2016-12-25 | 2017-05-31 | 河南师范大学 | Y type amphiphilic block copolymers and preparation method thereof and with the copolymer be carrier targeting intracellular drug release carrier micelle |
| CN106750343B (en) * | 2016-12-25 | 2020-07-03 | 河南师范大学 | Y-shaped amphiphilic block copolymer, preparation method thereof and drug-loaded micelle taking copolymer as carrier for targeting intracellular drug release |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| ES2211028T3 (en) | NEW TENSIOACTIVE COPOLYMERS BASED ON METHYLIDENE MALONATE. | |
| CN101665576B (en) | Microgel based on cyclodextrins and preparation method thereof | |
| CN101684174B (en) | Amphiphilic biologically degradable polyester comb-grafted copolymer and temperature-sensitive situ-gel system thereof | |
| CN102030871B (en) | Polyethylene glycol block biodegradable polyester comb-type graft copolymer, and preparation method and application thereof | |
| CN103254442B (en) | Disulfide bond linked polyester comb-type graft copolymer as well as preparation method and application thereof | |
| Liu et al. | Thermally responsive polymeric micellar nanoparticles self-assembled from cholesteryl end-capped random poly (N-isopropylacrylamide-co-N, N-dimethylacrylamide): synthesis, temperature-sensitivity, and morphologies | |
| CN104231155B (en) | Cholesterol modifies amphipathic pH response brush copolymer and preparation and micella thereof | |
| CN100439421C (en) | Thermosensitive poly (organophosphazenes), preparation method thereof and injectable thermosensitive polyphosphazene hydrogels using the same | |
| Shao et al. | Synthesis and characterization of amphiphilic poly (ɛ-caprolactone)-b-polyphosphoester diblock copolymers bearing multifunctional pendant groups | |
| CN102030898B (en) | ABC-type amphiphilic biodegradable polyester triblock copolymer and preparation method and application thereof | |
| CN107669626B (en) | Preparation method and application of high drug-loading reduction-sensitive drug delivery system | |
| CN103554508B (en) | Acid-sensitive amphipathic star-block copolymers, its preparation method and application | |
| CN102268137A (en) | Star-shaped polylactic acid-poly(dimethylaminoethyl methacrylate) amphiphilic segmented copolymer and preparation method thereof | |
| US20180325820A1 (en) | Biocompatible water-soluble polymers including sulfoxide functionality | |
| CN107641201B (en) | Preparation method and application of block copolymer containing double selenium bonds with rapid oxidation/reduction dual responsiveness | |
| CN101288782B (en) | Preparation method of high intensity biodegradable supramolecule hydrogel | |
| KR20180068852A (en) | Composition of amphiphilic block copolymer with improved micelle stability and pharmaceutical composition comprising the same | |
| CN103159959B (en) | Star-like amphipathic multipolymer of a kind of M-PLGA-TPGS and preparation method thereof and application | |
| CN110423337B (en) | Temperature-sensitive supramolecular polymer regulated and controlled by multiple hydrogen bonds and preparation method thereof | |
| Cajot et al. | Novel functional degradable block copolymers for the building of reactive micelles | |
| CN100389140C (en) | Method of preparing nanometer and micron self assembling body from poly peptide-b-polytetrahydrofuran-b-polypeptide triblock copolymer | |
| CN102212198B (en) | Double-arm star polylactic acid-polydimethylaminoethyl methacrylate amphiphilic block copolymer and preparation method thereof | |
| Afgan et al. | Studies on non-gelatinous & thermo-responsive chitosan with the N-isopropylacrylamide by RAFT methodology for control release of levofloxacin | |
| CN102212197B (en) | Hyperbranched star polylactic acid-polydimethylaminoethyl methacrylate amphiphilic block copolymer and preparation method thereof | |
| US20190023852A1 (en) | Branched polyester carrying dendrons |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20111207 |
|
| C20 | Patent right or utility model deemed to be abandoned or is abandoned |